Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX ¼ β-IEPOX þ δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low-and high-NO x conditions, respectively. Isoprene low-NO x SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NO x conditions, isoprene SOA formation occurs through oxidation of its secondgeneration product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NO x SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO 2 and NO 2 , respectively) could be a substantial source of "missing urban SOA" not included in current atmospheric models.acid-catalyzed particle-phase reactions | epoxides | methacryloylperoxynitrate | organosulfates I soprene (2-methyl-1,3-butadiene, C 5 H 8 ) is the most abundant nonmethane hydrocarbon emitted into the Earth's atmosphere, with emissions estimated to be 440-660 TgC yr −1 (1). The atmospheric hydroxyl (OH) radical-initiated oxidation of isoprene, so-called photooxidation, plays a key role in establishing the balance of hydrogen oxide (HO x ¼ OH þ HO 2 ) radicals in vegetated areas (2, 3) and influences urban ozone formation in populated areas blanketed with biogenic emissions (4). Formation of low-volatility compounds during isoprene oxidation has been estimated to be the single largest source of atmospheric organic aerosol [i.e., secondary organic aerosol (SOA)] (5-8).The photooxidation of unsaturated volatile organic compounds (VOCs) proceeds through formation of a hydroxy peroxy (RO 2 ) radical, the fate of which depends on the concentration of nitrogen oxides (NO x ¼ NO þ NO 2 ). Higher SOA yields from isoprene are observed under low-NO x (or NO x -free) conditions; in this regime, RO 2 radicals react primarily with HO 2 , a pathway that tends to produce lower-volatility oxidation products than that involving the reaction of RO 2 with NO (9-11). Under high-NO x conditions, RO 2 radicals react with NO to produce alkoxy (RO) radicals, or as a minor pathway, organic nitrates (RONO 2 ). For small VOCs (≤C 10 ), like isoprene, these RO radicals generally fragment into smaller more volatile products, resulting in small amounts of SOA (9-11). Despite the fact that SOA from isoprene has been extensively studied (8), the chemical pathways to its formation under both low-and high-NO x conditions have remained unclear. In this study we examine the mechanism of isoprene SOA formation in these two ...

Abstract. The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40–75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm−1 (−50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.

Abstract. The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (< 10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particlephase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C₄-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO₂ enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO₂/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO₂ conditions, as PAN (peroxy acyl nitrate, RC(O)OONO₂) formation is structurally unfavorable. At atmospherically relevant NO₂/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO₂/NO ratios. At sufficiently high NO₂ concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO₂ can exceed that from RO₂+HO₂ reactions under the same inorganic seed conditions, making RO₂+NO₂ an important channel for SOA formation